JP6392562B2 - Water-in-oil emulsified cosmetic - Google Patents

Description

  The present invention relates to a water-in-oil emulsified cosmetic.

Conventionally, cosmetics excellent in feeling of use such as makeup sustainability, spread, and stickiness suppression have been studied using various polymers and the like.
For example, Patent Document 1 describes a cosmetic containing a fluorine-modified silicone resin having a silanol group in the molecule and having a specific structure, is difficult to collapse, has high water resistance, and has a long-lasting cosmetic effect. It has been proposed to be superior. Patent Document 2 discloses water-in-oil containing a fluorine-modified silicone resin having a silanol group in the molecule and a specific structure, a specific treated powder, and a poly (N-acylalkylenimine) -modified organopolysiloxane. It is described that the type emulsified cosmetic can be uniformly attached to the skin, does not cause color unevenness, and provides a natural finish.
Furthermore, Patent Document 3 describes a water-in-oil emulsified cosmetic containing a vinyl polymer having a carbosiloxane dendrimer structure in the side chain, a specific nonvolatile oil agent, and a hydrophobized powder. It has good properties, good spreading, little stickiness, and a feeling of use that has a little uncomfortable feeling such as a film feeling, is excellent in the effect of making the unevenness of the skin inconspicuous, has a good makeup sustainability, and the unevenness of the unevenness over time It is described that is difficult to occur.

Japanese Patent Laid-Open No. 9-12431 JP 2013-256451 A JP 2010-18612 A

  Conventional cosmetics containing a silanol group-containing fluorine-modified silicone resin having a specific structure and a vinyl polymer having a carbosiloxane dendrimer structure in the side chain are water repellency, oil repellency, makeup persistence, during application Excellent in terms of spreading and stickiness control. Recently, however, there is a need for overcoating as a foundation that cleanses skin problems and makes the skin look clean, and there is little sense of wrinkle immediately after application, and when the foundation is overlaid, the sponge slips smoothly and overlaid. However, there is a need for cosmetics that do not have a squeaky or stiff feel and can be finished with a single application.

  By using a vinyl polymer having a carbosiloxane dendrimer structure in the side chain, a specific fluorine-modified silicone resin and an ester oil in combination at a specific ratio, the present inventors do not become lumpy immediately after coating, It has been found that a water-in-oil emulsified cosmetic is obtained that has no stickiness, suppresses the sticking of the sponge when the foundation is overlaid, makes the makeup, and the finished powder spray is not noticeable.

The present invention includes the following components (A), (B) and (C):
(A) 0.1-20% by mass of a vinyl polymer having a carbosiloxane dendrimer structure in the side chain,
(B) The following general formula (3)
R ²¹ _g SiO _{(4-g) / 2} (3)
(In the formula, R ²¹ represents a hydrocarbon group having 1 to 8 carbon atoms, a phenyl group, a hydroxyl group, or a general formula —R ²² —Rf (R ²² represents a divalent alkylene group having 2 to 6 carbon atoms, and Rf represents carbon A perfluoroalkyl group having a number of 1 to 8), which is arbitrarily selected from hydroxyl groups and functional groups having the general formula -R ²² -Rf as essential, and g is an average number of 1.0 ≦ g ≦ 1. 8)
0.01 to 20% by mass of a fluorine-modified silicone resin having a structure represented by
(C) It relates to a water-in-oil emulsified cosmetic containing an ester oil that is liquid at 25 ° C. and having a mass ratio (A) / (B) of component (A) to component (B) of 0.08 to 10. .

The water-in-oil emulsified cosmetic of the present invention does not become lumpy immediately after application, does not feel stiff, suppresses the sticking of the sponge when the foundation is overlaid, and does not stand out in the makeup and the powdered finish. . Also, it can be finished with a single coat.
It should be noted that “to become lumpy immediately after application” means that when applied to the skin, it does not spread quickly but stays in one place and becomes uneven. Also, finishing with a single application means that the cosmetic can be applied at one time without reapplying the same part of the skin many times when spreading the cosmetic on the skin. By realizing this, it is possible to suppress the deterioration of the finish and the occurrence of color unevenness due to repainting.

  In the vinyl polymer having a carbosiloxane dendrimer structure as a component (A) in the side chain used in the present invention, the carbosiloxane dendrimer structure is preferably a group represented by the following formula (1).

In the formula, Z is a divalent organic group, p is 0 or 1, and R ¹ is an alkyl group having 1 to 10 carbon atoms or an aryl group. X ¹ is a silylalkyl group represented by the following formula when i = 1.

In the formula, R ¹ is the same as described above, R ² is an alkylene group having 2 to 10 carbon atoms, R ³ is an alkyl group having 1 to 10 carbon atoms, X ^{i + 1} is a hydrogen atom, It is a group selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, an aryl group, and the silylalkyl group. i is an integer of 1 to 10 indicating the hierarchy of the silylalkyl group, and a ⁱ is an integer of 0 to 3.

  In formula (1), Z is a divalent organic group, alkylene group, arylene group, aralkylene group, ester-containing divalent organic group, ether-containing divalent organic group, ketone-containing divalent organic group, amide group-containing 2 A valent organic group is exemplified. Among these, an organic group represented by the following formula is preferable.

In the formula, R ⁹ is an alkylene group having 1 to 10 carbon atoms, and examples thereof include a methylene group, an ethylene group, a propylene group, and a butylene group. Among these, an ethylene group and a propylene group are preferable. R ¹⁰ is an alkyl group having 1 to ¹⁰ carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, and a butyl group. Among these, a methyl group is preferable. R ¹¹ is an alkylene group having 1 to 10 carbon atoms, and examples thereof include alkylene groups such as a methylene group, an ethylene group, a propylene group, and a butylene group. Among these, an ethylene group is preferable. d is an integer of 0 to 4, and e is 0 or 1.

In the formula (1), R ¹ is an alkyl group or aryl group having 1 to 10 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, an isopropyl group, and isobutyl. Group, cyclopentyl group, and cyclohexyl group are exemplified, and as aryl group, phenyl group and naphthyl group are exemplified. Among these, a methyl group and a phenyl group are preferable, and a methyl group is particularly preferable.
X ¹ is a silylalkyl group represented by the following formula when i = 1.

In the formula, R ¹ is the same as described above. R ² is an alkylene group having 2 to 10 carbon atoms, and a linear alkylene group such as an ethylene group, a propylene group, a butylene group, or a hexylene group; a methylmethylene group, a methylethylene group, a 1-methylpentylene group, 1 And a branched alkylene group such as 1,4-dimethylbutylene group. Among these, an ethylene group, a methylethylene group, a hexylene group, a 1-methylpentylene group, and a 1,4-dimethylbutylene group are preferable. R ³ is an alkyl group having 1 to 10 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, and an isopropyl group. X ^{i + 1} is a group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group, and the silylalkyl group. a ⁱ is an integer of 0-3. i is an integer of 1 to 10, which indicates the number of layers of the silylalkyl group, that is, the number of repetitions of the silylalkyl group.

  As the vinyl polymer of component (A), 0 to 99.9 parts by mass of vinyl monomers other than (A1) and (A2), and (A2) general formula (2):

(In the formula, Y is an organic group capable of radical polymerization, and R ¹ and X ¹ are the same as described above.)
A vinyl polymer containing a carbosiloxane dendrimer structure obtained by (co) polymerizing 100 to 0.1 parts by mass of a carbosiloxane dendrimer having an organic group capable of radical polymerization represented by

In the above formula, Y is an organic group capable of radical polymerization, and R ¹ is an alkyl or aryl group having 1 to 10 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, an isopropyl group, an isobutyl group, a cyclopentyl group, and a cyclohexyl group. Examples of the aryl group include a phenyl group and a naphthyl group. Among these, a methyl group and a phenyl group are preferable, and a methyl group is particularly preferable.

  In this vinyl polymer, the vinyl monomer as the component (A1) is not particularly limited as long as it has a radical polymerizable vinyl group. Examples of such vinyl monomers include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, Lower alkyl (meth) acrylates such as isobutyl (meth) acrylate, tert-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate; 2-ethylhexyl (meth) acrylate, ( Higher alkyl (meth) acrylates such as octyl acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate; vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caproate, vinyl 2-ethylhexanoate, laurin Fatty acid vinyl esters such as vinyl acid vinyl and vinyl stearate; Aromatic monomers such as len, vinyltoluene, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate; (meth) acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, isobutoxy Amide group-containing vinyl monomers such as methoxy (meth) acrylamide, N, N-dimethyl (meth) acrylamide, vinylpyrrolidone, N-vinylacetamide; hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, Hydroxyl-containing vinyl monomers such as glyceryl (meth) acrylate and hydroxyethylacrylamide; (meth) acrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid and other carboxylic acid-containing vinyl monomers and their salts ; Tetrahydroflu Ether linkages such as ril (meth) acrylate, butoxyethyl (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, polyethylene glycol (meth) acrylate, polypropylene glycol mono (meth) acrylate, hydroxybutyl vinyl ether, cetyl vinyl ether, 2-ethylhexyl vinyl ether Containing vinyl-type monomer; Reactive group-containing monomer such as (meth) acrylic acid glycidyl, (meth) allyl glycidyl ether, methacryloyloxyethyl isocyanate, (meth) acryloxypropyltrimethoxysilane; (meth) acrylic at one end Macromonomers such as polydimethylsiloxane containing a group, polydimethylsiloxane containing a styryl group at one end; butadiene; vinyl chloride; salt (Meth) acrylonitrile; dibutyl fumarate; maleic anhydride; radical polymerizable unsaturated monomers having sulfonic acid groups such as styrenesulfonic acid, acrylamide-2-methylpropanesulfonic acid, and alkali metals thereof Salts, ammonium salts, organic amine salts; quaternary ammonium salts derived from (meth) acrylic acid such as 2-hydroxy-3-methacryloxypropyltrimethylammonium chloride; tertiary amino groups such as diethylaminoethyl methacrylate Examples thereof include methacrylic acid esters of alcohol, vinyl pyridine and quaternary ammonium salts thereof.

  Polyfunctional vinyl monomers can also be used. For example, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, ethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate , Polyethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane trioxyethyl (meta ) Acrylate, tris (2-hydroxyethyl) isocyanurate di (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, styryl-blocked polydimethylsiloxane, etc. Saturated group containing silicone - emission compounds and the like.

  The component (A2) carbosiloxane dendrimer is not particularly limited as long as it has an organic group capable of radical polymerization represented by the general formula (2). In general formula (2), Y is an organic group capable of radical polymerization, and any organic group capable of radical reaction may be used. Specifically, a (meth) acryloxy group-containing organic group represented by the following general formula , (Meth) acrylamide group-containing organic groups, styryl group-containing organic groups, alkenyl groups having 2 to 10 carbon atoms, and the like.

Wherein R ⁴ and R ⁶ are a hydrogen atom or a methyl group, R ⁵ and R ⁸ are alkylene groups having 1 to 10 carbon atoms, and R ⁷ is an alkyl group having 1 to 10 carbon atoms. B is an integer from 0 to 4 and c is 0 or 1.)

  Examples of such radically polymerizable organic groups include 2-acryloyloxyethyl group, 3-acryloyloxypropyl group, 2-methacryloyloxyethyl group, 3-methacryloyloxypropyl group, 4-vinylphenyl group, 3-vinylphenyl group, Vinylphenyl group, 4- (2-propenyl) phenyl group, 3- (2-propenyl) phenyl group, 2- (4-vinylphenyl) ethyl group, 2- (3-vinylphenyl) ethyl group, vinyl group, allyl Group, methallyl group, and 5-hexenyl group.

  In the general formula (2), when i = 1, that is, the number of silylalkyl groups is 1, the carbosiloxane dendrimer of the component (A2) has the general formula:

(Wherein, Y, R ^1, R ² and R ³ are as defined above, but .a ¹ R ¹² is the same as the hydrogen atom or the R ¹ is the same as the a ^i, in one molecule The average total number of a ¹ is 0 to 7.)
Examples of such carboxydendrimers (A2) containing radically polymerizable organic groups include carbosiloxane dendrimers represented by the following average composition formula.

  Such carbosiloxane dendrimers can be produced, for example, according to the production methods described in JP-A Nos. 11-1530 and 2000-63225.

  In the vinyl polymer containing a dendrimer structure used in the present invention, the mass ratio of the component (A1) to the component (A2) is (A1) :( A2) = 0: 100 to 99.9: 0.1. Is preferably 5:95 to 90:10, more preferably 10:90 to 80:20.

  The number average molecular weight of the vinyl polymer having a carbosiloxane dendrimer structure as the component (A) used in the present invention is preferably 3,000 to 2,000,000 from the ease of blending as a cosmetic raw material. More preferably, it is 5,000 to 800,000. Further, the property may be any of liquid, gum, paste, solid, etc. at 25 ° C., but from the viewpoint of the durability of the resulting cosmetic film, a solid one is preferred. Further, from the viewpoint of compoundability, a solution or dispersion diluted with a solvent is preferable. Among these, from the viewpoint of dispersibility in cosmetics and workability, it is preferably used as a dispersion diluted with liquid oil, preferably silicone oil or hydrocarbon oil, dimethylpolysiloxane, decamethylcyclohexane. It is more preferable to use pentasiloxane or isododecane.

  As the vinyl polymer having a carbosiloxane dendrimer structure in the side chain, a silicone dendrimer / acrylic copolymer is preferable, FA4001CM (decamethylcyclopentasiloxane solution), FA4002ID (isododecane solution) (above, manufactured by Toray Dow Corning) ) Etc. can be used.

  The component (A) can be used alone or in combination of two or more, and the content is 0.1% by mass or more in the total composition from the viewpoint of excellent adhesion of the cosmetic to the skin. 5 mass% or more is preferable, 1 mass% or more is more preferable, it is 20 mass% or less, 8 mass% or less is preferable, and 4 mass% or less is more preferable. Moreover, content of a component (A) is 0.1-20 mass% in the whole composition, 0.5-8 mass% is preferable, and 1-4 mass% is more preferable.

The component (B) fluorine-modified silicone resin used in the present invention has a structure represented by the general formula (3).
The fluorine-modified silicone resin has a silanol group in the molecule from the viewpoint of adhesion to skin and powder, and the ratio of the OH group in the silanol group is 0.1 to 5% by mass with respect to the resin mass. Of 0.5 to 5% by mass is more preferable.

  The fluorine-modified silicone resin is solid at 25 ° C. For this reason, it is preferable to use it by dissolving in cyclic silicone, dimethylpolysiloxane or the like. The cyclic silicone is preferably used by dissolving in one or more selected from octamethylcyclotetrasiloxane (D4) and decamethylcyclopentasiloxane (D5).

  As such a fluorine-modified silicone resin, INCI names “Trifluoropropyldimethyl / Trimethylsiloxysilicate”, XS66-B8226, XS66-C1191, XS66-B8636 (above, Momentive Performance Materials) Commercially available products such as those manufactured by KK

  Component (B) can be used singly or in combination of two or more, and the content is 0.01 mass in the total composition from the viewpoint of uniformly adhering cosmetics to the skin and improving adhesion. % Or more, preferably 0.5% by weight or more, more preferably 2% by weight or more, further preferably 3% by weight or more, 20% by weight or less, preferably 8% by weight or less, and further preferably 5% by weight or less. preferable. Moreover, content of a component (B) is 0.01-20 mass% in all the compositions, 0.5-8 mass% is preferable, 2-5 mass% is more preferable, 3-5 mass% is Further preferred.

  In the present invention, the mass ratio (A) / (B) of the components (A) and (B) suppresses the occurrence of unevenness in the cosmetic during application, and suppresses the occurrence of streak immediately after application and the feeling of stiffness. When the foundation is overlaid, it prevents the sponge from getting stuck, reduces the noticeable makeup and powder finish, and repaints the same part of the skin over and over when applying cosmetics to the skin. Without being less than 0.08, 0.1 or more, preferably 0.2 or more, more preferably 0.3 or more, further preferably 10 or less, and 5 or less. Is preferable, 1 or less is more preferable, and 0.7 or less is more preferable. Moreover, mass ratio (A) / (B) of component (A) and (B) is 0.08-10, 0.1-5 are preferable, 0.2-1 are more preferable, 0.3 -0.7 is more preferable.

  Component (C) is an ester oil that is liquid at 25 ° C. Here, the liquid state has fluidity, and includes pastes. In addition, the molecular weight of the component (C) ester oil is compatible with the vinyl polymer having a carbosiloxane dendrimer structure in the side chain, is excellent in adhesiveness, and is used in combination with the component (A) and the component (B). From the point which suppresses stickiness and is excellent in film property, 250-2000 are preferred, 300-1000 are more preferred, and 350-800 are still more preferred.

The ester oil that is liquid at 25 ° C. as the component (C) is preferably a monoester or a diester. Specifically, for example, isotridecyl isononanoate, diisostearyl malate, isostearyl myristate, neopentyl glycol dicaprate, Examples include diglyceryl diisostearate, glyceryl monoisostearate, 2-ethylhexyl paramethoxycinnamate, tocopherol acetate, and diglyceryl monoisostearate.
Of these, monoesters are more preferable, isotridecyl isononanoate, isostearyl myristate, glyceryl monoisostearate, 2-ethylhexyl paramethoxycinnamate, tocopherol acetate, and 2-ethylhexyl paramethoxycinnamate. More preferred is tocopherol acetate.

  Component (C) can be used singly or in combination of two or more, and from the viewpoint of suppressing stickiness and excellent film properties, the content is preferably 0.1% by mass or more in the total composition, 0 .2% by mass or more is more preferable, 0.4% by mass or more is more preferable, 1% by mass or more is more preferable, 30% by mass or less is preferable, 20% by mass or less is more preferable, and 10% by mass or less is more preferable. 7 mass% or less is still more preferable. In addition, the content of the component (C) is preferably 0.1 to 30% by mass, more preferably 0.2 to 20% by mass, further preferably 0.4 to 10% by mass, and 1 to 7% in the entire composition. A mass% is even more preferable.

  In the present invention, the total mass of the components (A) and (B) and the mass ratio of the component (C) ((A) + (B)) / (C) Suppresses the occurrence of lumps immediately after application and the feeling of stiffness, suppresses the sticking of the sponge when used with the foundation overlaid, suppresses the noticeable appearance of makeup shake and finished powder blowing, and applies cosmetics to the skin When spreading, it is preferably 0.1 or more, more preferably 0.2 or more, and even more preferably 0.5 or more, from the point that it can be finished with a single application without repainting the same part of the skin many times. 40 or less is preferable, 20 or less is more preferable, 10 or less is more preferable, and 8 or less is more preferable. In addition, the total mass of the components (A) and (B) and the mass ratio ((A) + (B)) / (C) of the component (C) are preferably 0.1 to 40, and 0.2 to 20 Is more preferable, 0.5 to 10 is more preferable, and 0.5 to 8 is still more preferable.

The water-in-oil emulsified cosmetic of the present invention can further contain (D) a fluorine-modified silicone that is liquid at 25 ° C., and can provide more excellent makeup sustainability. Here, the liquid state has fluidity, and includes pastes.
As such fluorine-modified silicone, the following general formulas (4) and (5)

(In the formula, Rf represents a linear or branched perfluoroalkyl group having 6 carbon atoms, and R ³¹ , R ³² and R ³³ are the same or different and each represents a linear or branched chain having 1 to 6 carbon atoms. Represents an alkyl group, m represents a number of 2 to 6, n represents a number of 1 to 6, p represents a number of 3 to 50, s represents a number of 1 to 5, and the ratio of p and s Is 0.66 ≦ p / (p + s) ≦ 0.9)
A fluorine-modified silicone having a polysiloxane unit represented by

In the formula, examples of the alkyl group represented by R ³¹ , R ³² and R ³³ include linear alkyl groups such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group; an isopropyl group, sec- Examples thereof include branched alkyl groups such as butyl group, tert-butyl group, neopentyl group and 1-ethylpropyl group; cyclic alkyl groups such as cyclopentyl and cyclohexyl.

Moreover, m shows the number of 2-6, Preferably it is 2-5, More preferably, it is 3. n shows the number of 1-6, Preferably it is 1-4, More preferably, it is 2.
p shows the number of 3-50, Preferably it is 3-10, More preferably, it is 3-6. s shows the number of 1-5, Preferably it is 1-3, More preferably, it is 1.

  Further, the ratio of p and s, that is, the modification ratio of the polysiloxane unit p represented by the general formula (4) to the total p + s of the polysiloxane units represented by the general formulas (4) and (5) is used. 0.66 ≦ p / (p + s) ≦ 0.9, and 0.75 ≦ from the viewpoint that it is excellent in feeling and makeup, is less likely to cause uneven appearance, and is less likely to cause uneven application after the cosmetic is applied. p / (p + s) ≦ 0.83 is preferable.

The fluorine-modified silicone of component (D) can be produced, for example, according to the method described in JP-A-6-184212.
As a fluorine-modified silicone of a component (D), what is represented by following General formula (6) is preferable.

(Wherein p and s have the same meaning as described above, and q represents a number of 5)

  Ingredient (D) can be used singly or in combination of two or more, and the content is 0.01 mass in the total composition from the standpoint of excellent makeup sustainability and suppressing noticeable makeup and finished powder blowing. % Or more, preferably 0.1% by weight or more, more preferably 0.2% by weight or more, more preferably 50% by weight or less, more preferably 30% by weight or less, and still more preferably 15% by weight or less. Moreover, 0.01-50 mass% is preferable in the whole composition, as for content of a component (D), 0.1-30 mass% is more preferable, 0.2-15 mass% is still more preferable.

  In the present invention, the content of water is preferably 10% by mass or more, more preferably 12% by mass or more, further preferably 14% by mass or more, preferably 70% by mass or less, and more preferably 50% by mass or less in the total composition. Preferably, 30 mass% or less is more preferable.

  The water-in-oil emulsified cosmetics of the present invention are components other than the above-mentioned components that are usually used in cosmetics, for example, oily components other than those described above, UV absorbers other than those described above, surfactants, pigments, water-soluble polymers. , Antioxidants, fragrances, pigments, preservatives, thickeners, pH adjusters, blood circulation promoters, cooling agents, antiperspirants, fungicides, skin activators, moisturizers, refreshing agents, etc. it can.

The water-in-oil emulsified cosmetic of the present invention can be produced according to a usual method, and can be made into a liquid, emulsion, paste, cream, gel, etc., emulsion, cream Is preferred.
The water-in-oil emulsified cosmetic of the present invention comprises a makeup base, foundation, concealer; makeup cosmetics such as blusher, eyeshadow, mascara, eyeliner, eyebrow, overcoat agent, lipstick; sunscreen emulsion, It can be applied as UV protection cosmetics such as sunscreen cream. Among these, a makeup base, a liquid foundation, and a concealer are more preferable.
The water-in-oil emulsified cosmetic of the present invention can be used in the case of using only a single product, or in the case of overlaying powder cosmetics such as liquid foundation, powder foundation, and white powder.

The water-in-oil emulsified cosmetic of the present invention preferably has a viscosity immediately after production at 25 ° C. of 500 to 15000 mPa · s, and preferably 1000 to 12000 mPa · s, from the viewpoint of excellent spreadability and excellent adhesion to the skin. s is more preferable, and 3000 to 7000 mPa · s is more preferable.
In the present invention, the viscosity is measured at 25 ° C. using a viscometer (manufactured by Toki Sangyo Co., Ltd., VISCOMETER TVB-10 viscometer, rotational speed 6 r / min, rotor No. 3, 1 min).
This invention discloses the following compositions further regarding embodiment mentioned above.

<1> The following components (A), (B) and (C):
(A) 0.1-20% by mass of a vinyl polymer having a carbosiloxane dendrimer structure in the side chain,
(B) The following general formula (3)
R ²¹ _g SiO _{(4-g) / 2} (3)
(In the formula, R ²¹ represents a hydrocarbon group having 1 to 8 carbon atoms, a phenyl group, a hydroxyl group, or a general formula —R ²² —Rf (R ²² represents a divalent alkylene group having 2 to 6 carbon atoms, and Rf represents carbon A perfluoroalkyl group having a number of 1 to 8), which is arbitrarily selected from hydroxyl groups and functional groups having the general formula -R ²² -Rf as essential, and g is an average number of 1.0 ≦ g ≦ 1. 8)
0.01 to 20% by mass of a fluorine-modified silicone resin having a structure represented by
(C) A water-in-oil emulsified cosmetic containing an ester oil that is liquid at 25 ° C. and having a mass ratio (A) / (B) of components (A) and (B) of 0.08 to 10.

<2> In the component (A), the carbosiloxane dendrimer structure has the following formula (1)

{In the formula, Z is a divalent organic group, p is 0 or 1, and R ¹ is an alkyl group or an aryl group having 1 to 10 carbon atoms. X ¹ is a silylalkyl group represented by the following formula when i = 1.

(In the formula, R ¹ is the same as above, R ² is an alkylene group having 2 to 10 carbon atoms, R ³ is an alkyl group having 1 to 10 carbon atoms, and X ^{i + 1} is a hydrogen atom. , A group selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, an aryl group, and the above silylalkyl group, i is an integer of 1 to 10 indicating the hierarchy of the silylalkyl group, a ⁱ is an integer from 0 to 3.)}
The water-in-oil emulsified cosmetic according to <1>, which is a group represented by the formula:
<3> Component (A) vinyl polymer is (A1) 0-99.9 parts by mass of vinyl monomer and (A2) general formula:

{Wherein Y is a radically polymerizable organic group, R ¹ is an alkyl group or aryl group having 1 to 10 carbon atoms, and X ¹ is a silylalkyl represented by the following formula when i = 1. It is a group.

(In the formula, R ¹ is the same as above, R ² is an alkylene group having 2 to 10 carbon atoms, R ³ is an alkyl group having 1 to 10 carbon atoms, and X ^{i + 1} is a hydrogen atom. , A group selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, an aryl group, and the above silylalkyl group, i is an integer of 1 to 10 indicating the hierarchy of the silylalkyl group, a ⁱ is an integer from 0 to 3.)}
The water-in-oil emulsified cosmetic according to <1> or <2>, wherein 100 to 0.1 parts by mass of a carbosiloxane dendrimer having an organic group capable of radical polymerization represented by formula (1) is polymerized.
<4> The organic group Y capable of radical polymerization in (A2) has the general formula

(In the formula, R ⁴ is a hydrogen atom or a methyl group, and R ⁵ is an alkylene group having 1 to 10 carbon atoms.)
An acrylic group or methacryl group-containing organic group represented by the general formula:

Wherein R ⁶ is a hydrogen atom or a methyl group, R ⁷ is an alkyl group having 1 to 10 carbon atoms, R ⁸ is an alkylene group having 1 to 10 carbon atoms, and b is 0 to 4 And c is 0 or 1.)
The water-in-oil emulsified cosmetic according to <3>, which is a group selected from the group consisting of a styryl group-containing organic group and an alkenyl group having 2 to 10 carbon atoms.
The content of <5> component (A) is preferably 0.5% by mass or more, more preferably 1% by mass or more, preferably 8% by mass or less, and more preferably 4% by mass or less in the total composition. The water-in-oil emulsified cosmetic according to any one of the above <1> to <4>.

<6> The water-in-oil type according to any one of <1> to <5>, wherein the fluorine-modified silicone resin of component (B) is preferably trifluoropropyldimethyl / trimethylsiloxysilicate. Emulsified cosmetic.
The content of <7> component (B) is preferably 0.5% by mass or more in the total composition, more preferably 2% by mass or more, further preferably 3% by mass or more, and 8% by mass or less. The water-in-oil emulsified cosmetic according to any one of <1> to <6>, preferably 5% by mass or less.
<8> The mass ratio (A) / (B) of the components (A) and (B) is preferably 0.1 or more, more preferably 0.2 or more, still more preferably 0.3 or more, 5 or less is preferable, 1 or less is more preferable, and 0.7 or less is more preferable, The water-in-oil type emulsified cosmetic according to any one of the above <1> to <7>.

<9> The molecular weight of the component (C) is preferably 250 to 2000, more preferably 300 to 1000, and further preferably 350 to 800, in the oil according to any one of the above <1> to <8> Water-type emulsified cosmetic.
<10> The ester oil of component (C) is preferably a monoester or a diester, more preferably a monoester, isotridecyl isononanoate, isostearyl myristate, glyceryl monomystearate, paramethoxy cinnamon The water-in-oil emulsion cosmetic according to any one of <1> to <8>, wherein 2-ethylhexyl acid and tocopherol acetate are more preferable, and 2-ethylhexyl paramethoxycinnamate and tocopherol acetate are more preferable.
The content of the <11> component (C) is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, still more preferably 0.4% by mass or more, in the total composition. Any of the above <1> to <10>, more preferably not less than 30% by weight, more preferably not more than 30% by weight, more preferably not more than 20% by weight, still more preferably not more than 10% by weight, and still more preferably not more than 7% by weight. 1. A water-in-oil emulsified cosmetic according to 1.

<12> The total mass of the components (A) and (B) and the mass ratio ((A) + (B)) / (C) of the component (C) are preferably 0.1 or more and 0 2 or more is more preferable, 0.5 or more is more preferable, 40 or less is preferable, 20 or less is more preferable, 10 or less is more preferable, and 8 or less is more preferable, any one of the above <1> to <11> The water-in-oil emulsified cosmetic described.
<13> The water-in-oil emulsified cosmetic according to any one of <1> to <12>, further comprising (D) a fluorine-modified silicone that is liquid at 25 ° C.
<14> Component (D) is preferably the following general formulas (4) and (5)

(In the formula, Rf represents a linear or branched perfluoroalkyl group having 6 carbon atoms, and R ³¹ , R ³² and R ³³ are the same or different and each represents a linear or branched chain having 1 to 6 carbon atoms. Represents an alkyl group, m represents a number of 2 to 6, n represents a number of 1 to 6, p represents a number of 3 to 50, s represents a number of 1 to 5, and the ratio of p and s Is 0.66 ≦ p / (p + s) ≦ 0.9)
The water-in-oil emulsified cosmetic according to <13>, wherein the fluorine-modified silicone having a polysiloxane unit represented by formula (6) is more preferred.

(Wherein p and s have the same meaning as described above, and q represents a number of 5)

The content of <15> component (D) is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, still more preferably 0.2% by mass or more, in the total composition, 50 The water-in-oil emulsified cosmetic according to the above <13> or <14>, preferably at most mass%, more preferably at most 30 mass%, further preferably at most 15 mass%.
The content of <16> water is preferably 10% by mass or more in the total composition, more preferably 12% by mass or more, further preferably 14% by mass or more, and preferably 70% by mass or less, 50% by mass. The water-in-oil emulsified cosmetic according to any one of <1> to <15>, wherein the following is more preferable, and more preferably 30% by mass or less.
<17> The viscosity immediately after production at 25 ° C. is preferably 500 to 15000 mPa · s, more preferably 1000 to 12000 mPa · s, and further preferably 3000 to 7000 mPa · s. The water-in-oil emulsion cosmetic according to any one of the above.

Synthesis Example 1 (Synthesis of fluorine-modified silicone)

Synthesis of _{C 6 F 13 -CH 2 CH 2} -O-CH 2 CH = CH 2:
To a 2 L four-necked flask equipped with a thermometer and a cooling tube, 800 g (2.2 mol) of FA-6 (Unimatec) and 175.78 g (4.4 mol) of granular NaOH (Wako Pure Chemical Industries) were added. It was. While stirring at 200 rpm with a 12 cm crescent stirring blade made of Teflon (registered trademark) in a nitrogen atmosphere, the temperature in the flask was adjusted to 60 ° C. Thereto, 398.73 g (3.3 mol) of allyl bromide (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise over 2 hours. After completion of dropping, the mixture was stirred at 70 ° C. for 1 hour and at 80 ° C. for 1 hour. Thereafter, the temperature was raised to 130 ° C. to remove excess allyl bromide. After cooling to 60 ° C., 800 g of ion-exchanged water was added, stirred for 30 minutes, and then allowed to stand to separate the layers. The upper aqueous layer was extracted, and 800 g of ion-exchanged water was further added, followed by stirring, standing still, and removal of the aqueous layer. Dried at 60 ℃ / 5KPa, 100 ℃ / distilled at 2 KPa, as a fraction, to obtain a _{C 6 F 13 -CH 2 CH 2} -O-CH 2 CH = CH 2 774.9g ( yield: 88 %).

  To a 300 mL four-necked flask equipped with a thermometer, 52.89 g (111 mmol) of hydrogen polysiloxane (Shin-Etsu Chemical Co., Ltd.) represented by the following formula was added, and Teflon (registered trademark) 8 cm crescent moon was added under a nitrogen atmosphere. The mixture was stirred with a blade at 200 rpm, 2% by mass of chloroplatinic acid hexahydrate / isopropyl alcohol 0.66 g was added, and the temperature was raised to 110 ° C.

C ₆ F ₁₃ —CH ₂ CH ₂ —O—CH ₂ CH═CH ₂ 197.11 g (488 mmol) was added dropwise over 2 hours. After completion of dropping, the mixture was stirred at 110 ° C. for 2 hours. Thereafter, the temperature was lowered to 70 ° C. 25.07 g of 0.1% NaOH solution was added and stirred for 2 hours. After dehydration at 60 ° C./5 KPa, 2.51 g of carborane 3 (manufactured by Nippon Environmental Chemicals) was added at the same temperature, and the mixture was stirred for 2 hours. The mixture was filtered through a 0.1 μm PTFE membrane filter, and the filtrate was subjected to steam distillation using 100 ° C./5 KPa and 62.5 g of water to obtain 206.3 g of the target compound (Compound D1) (yield 89%).

Examples 1-9 and Comparative Examples 1-4
Manufactures water-in-oil emulsified cosmetics with the composition shown in Table 1 and is finished with a single application. It is difficult to become lumpy immediately after application, it is easy to slip during application, there is no feeling of wrinkle immediately after application, powder foundation application The initial absence of sponges, the absence of makeup after 6 hours of application of the powder foundation, and the absence of dusting after 6 hours of application of the powder foundation were evaluated. The results are also shown in Table 1.

(Manufacturing method)
The powder phase component was mixed and ground, added to the separately mixed oil phase component, and dispersed with a disper. Then, the water phase component was added, dispersed with a disper, and then stirred with a homomixer to obtain a water-in-oil emulsified cosmetic.

(Evaluation method)
(I) When applying each water-in-oil emulsified cosmetic to the skin, it is possible to apply the cosmetic without re-applying the same part of the skin many times. It was evaluated with. In addition, the evaluation result in a table | surface was sensory-evaluated by 10 expert evaluators in the following five steps, and was shown by the total score of 10 people.
5: There is no re-coating during application, and it is quickly finished with a single application.
4; There is almost no re-coating during application, and it is finished with a single application.
3: Finished while partially repainting during application.
2: Finishing over time and the number of times of application while recoating during application.
1; Application cannot be performed well, and application time and frequency are very long.

(II) It was evaluated that it was difficult to become lumpy immediately after application of each water-in-oil emulsified cosmetic, ease of slipping during application, and lack of stiffness immediately after application. In addition, the evaluation result in a table | surface was sensory-evaluated by 10 expert evaluators in the following five steps, and was shown by the total score of 10 people.

(1) Difficult to become lumps immediately after application:
5; No lumps.
4; Slight lumps are seen.
3; Dama is slightly noticeable.
2; Dama stands out.
1; Dama is quite noticeable.

(2) Ease of slipping during application:
5: Sliding during application is quite good.
4; Good sliding during application.
3; Slip during application is slightly good.
2: Sliding during application is bad.
1; Slip during application is considerably poor.

(3) No stiffness immediately after application:
5; I feel that there is no sense of stiffness immediately after application.
4; I feel that there is almost no stiffness immediately after application.
3; Feels somewhat stiff immediately after application.
2; Feels stiff immediately after application.
1; Feels very stiff immediately after application.

(III) After applying each water-in-oil emulsified cosmetic and finishing with powder foundation (Esto powder make-up active aura), there is no sponge caught in the initial stage of powder foundation application, after 6 hours of powder foundation application The lack of makeup and powdering were evaluated. In addition, the evaluation result in a table | surface was sensory-evaluated by 10 expert evaluators in the following five steps, and was shown by the total score of 10 people.

(4) Sponge is not caught in the initial stage of powder foundation application:
5: Feels not caught in the initial stage of application.
4; Almost no initial catching feeling.
3; A slight feeling of catching at the initial stage of application is felt.
2; Feeling a catch at the initial stage of application.
1; A feeling of catching at the initial stage of application is considerably felt.

(5) No makeup irregularity 5 hours after application of the powder foundation 5; no cosmetic irregularity.
4; Almost no makeup.
3; There is a little makeup twist.
2; There is makeup.
1; Shaking is remarkable.

(6) No powdering after 6 hours of powder foundation application:
5: No dusting is seen.
4; Slight dusting is seen.
3; Powder cleaning is slightly conspicuous.
2; Powdering is conspicuous.
1; Powder cleaning is quite conspicuous.

Claims (8)

The following components (A), (B) and (C):
(A) 0.1-20% by mass of a vinyl polymer having a carbosiloxane dendrimer structure in the side chain,
(B) The following general formula (3)
R ²¹ _g SiO _{(4-g) / 2} (3)
(In the formula, R ²¹ represents a hydrocarbon group having 1 to 8 carbon atoms, a phenyl group, a hydroxyl group, or a general formula —R ²² —Rf (R ²² represents a divalent alkylene group having 2 to 6 carbon atoms, and Rf represents carbon A perfluoroalkyl group having a number of 1 to 8), which is arbitrarily selected from hydroxyl groups and functional groups having the general formula -R ²² -Rf as essential, and g is an average number of 1.0 ≦ g ≦ 1. 8)
0.01 to 20% by mass of a fluorine-modified silicone resin having a structure represented by
(C) A water-in-oil emulsified cosmetic containing an ester oil that is liquid at 25 ° C. and having a mass ratio (A) / (B) of components (A) and (B) of 0.08 to 10. In component (A), the carbosiloxane dendrimer structure has the following formula (1)

{In the formula, Z is a divalent organic group, p is 0 or 1, and R ¹ is an alkyl group or an aryl group having 1 to 10 carbon atoms. X ¹ is a silylalkyl group represented by the following formula when i = 1.

(In the formula, R ¹ is the same as above, R ² is an alkylene group having 2 to 10 carbon atoms, R ³ is an alkyl group having 1 to 10 carbon atoms, and X ^{i + 1} is a hydrogen atom. , A group selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, an aryl group, and the above silylalkyl group, i is an integer of 1 to 10 indicating the hierarchy of the silylalkyl group, a ⁱ is an integer from 0 to 3.)}
The water-in-oil emulsified cosmetic according to claim 1, wherein Component (A) vinyl polymer comprises (A1) 0-99.9 parts by weight of vinyl monomer and (A2) general formula:

{Wherein Y is a radically polymerizable organic group, R ¹ is an alkyl group or aryl group having 1 to 10 carbon atoms, and X ¹ is a silylalkyl represented by the following formula when i = 1. It is a group.

(In the formula, R ¹ is the same as above, R ² is an alkylene group having 2 to 10 carbon atoms, R ³ is an alkyl group having 1 to 10 carbon atoms, and X ^{i + 1} is a hydrogen atom. , A group selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, an aryl group, and the above silylalkyl group, i is an integer of 1 to 10 indicating the hierarchy of the silylalkyl group, a ⁱ is an integer from 0 to 3.)}
The water-in-oil emulsion cosmetic according to claim 1 or 2, wherein 100 to 0.1 parts by mass of a carbosiloxane dendrimer having an organic group capable of radical polymerization represented by formula (1) is polymerized. The radically polymerizable organic group Y in (A2) has the general formula

(In the formula, R ⁴ is a hydrogen atom or a methyl group, and R ⁵ is an alkylene group having 1 to 10 carbon atoms.)
An acrylic group or methacryl group-containing organic group represented by the general formula:

Wherein R ⁶ is a hydrogen atom or a methyl group, R ⁷ is an alkyl group having 1 to 10 carbon atoms, R ⁸ is an alkylene group having 1 to 10 carbon atoms, and b is 0 to 4 And c is 0 or 1.)
The water-in-oil emulsified cosmetic according to claim 3, which is a group selected from the group consisting of a styryl group-containing organic group and an alkenyl group having 2 to 10 carbon atoms.   Content of a component (C) is 0.1-30 mass%, The water-in-oil type emulsified cosmetics of any one of Claims 1-4.   The total mass of the components (A) and (B) and the mass ratio ((A) + (B)) / (C) of the component (C) are 0.1 to 40. 2. A water-in-oil emulsified cosmetic according to item 1.   The water-in-oil emulsified cosmetic according to any one of claims 1 to 6, further comprising (D) a fluorine-modified silicone that is liquid at 25 ° C. (D) Fluorine-modified silicone that is liquid at 25 ° C. has the following general formulas (4) and (5)

(In the formula, Rf represents a linear or branched perfluoroalkyl group having 6 carbon atoms, and R ³¹ , R ³² and R ³³ are the same or different and each represents a linear or branched chain having 1 to 6 carbon atoms. Represents an alkyl group, m represents a number of 2 to 6, n represents a number of 1 to 6, p represents a number of 3 to 50, s represents a number of 1 to 5, and the ratio of p and s Is 0.66 ≦ p / (p + s) ≦ 0.9)
The water-in-oil emulsified cosmetic according to claim 7, which is a fluorine-modified silicone having a polysiloxane unit represented by: